CN117178384A - Negative electrode for secondary battery, and method for manufacturing negative electrode for secondary battery - Google Patents
Negative electrode for secondary battery, and method for manufacturing negative electrode for secondary battery Download PDFInfo
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- CN117178384A CN117178384A CN202280028935.3A CN202280028935A CN117178384A CN 117178384 A CN117178384 A CN 117178384A CN 202280028935 A CN202280028935 A CN 202280028935A CN 117178384 A CN117178384 A CN 117178384A
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- negative electrode
- secondary battery
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
A negative electrode for a secondary battery according to an aspect of the present disclosure includes: and a negative electrode composite material disposed on the negative electrode current collector, wherein the negative electrode composite material layer has a negative electrode active material containing a carbon material and a Si-based material, and the pore size distribution of the negative electrode composite material layer measured by mercury intrusion method has 2 peaks R1 and R2, wherein the peak R1 is 0.5 μm or more and 1.5 μm or less, the peak R2 is 2 μm or more and 10 μm or less, the average particle diameter of the Si-based material is 4 μm or more, and the content of the Si-based material is 30 mass% or more relative to the total amount of the negative electrode active material.
Description
Technical Field
The present disclosure relates to a negative electrode for a secondary battery, and a method for manufacturing a negative electrode for a secondary battery.
Background
As a material capable of realizing a high capacity of a battery, a Si-based material is attracting attention. The Si-based material is a material that can electrochemically store and release lithium ions, and can be charged and discharged with a very large capacity as compared with a carbon material such as graphite.
For example, patent document 1 discloses a negative electrode active material for a lithium ion secondary battery, which comprises: an Si-based material represented by SiOx (0 < x < 2) and a carbon material, wherein the negative electrode active material for a lithium ion secondary battery has pores inside.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2013-219059
Disclosure of Invention
Problems to be solved by the invention
However, si-based materials can achieve a higher capacity of secondary batteries, and conversely, expansion of the negative electrode and further degradation of charge-discharge cycle characteristics are problematic. In the technique of patent document 1, although degradation of charge-discharge cycle characteristics can be suppressed, further improvement is desired.
Accordingly, it is an object of the present disclosure to provide: a negative electrode for a secondary battery, and a method for manufacturing a negative electrode for a secondary battery, wherein the negative electrode has a high capacity, and wherein expansion of the negative electrode is suppressed, and further, degradation of charge-discharge cycle characteristics is suppressed.
Solution for solving the problem
A negative electrode for a secondary battery according to an aspect of the present disclosure includes: and a negative electrode composite material layer disposed on the negative electrode current collector, wherein the negative electrode composite material layer has a negative electrode active material containing a carbon material and a Si-based material, and the pore size distribution of the negative electrode composite material layer measured by mercury intrusion method has 2 peaks R1 and R2, wherein the peak R1 is 0.5 μm or more and 1.5 μm or less, the peak R2 is 2 μm or more and 10 μm or less, the average particle diameter of the Si-based material is 4 μm or more, and the content of the Si-based material is 30 mass% or more with respect to the total amount of the negative electrode active material.
A secondary battery according to an aspect of the present disclosure is characterized by comprising the negative electrode for a secondary battery.
The method for manufacturing a negative electrode for a secondary battery according to an embodiment of the present disclosure is characterized by comprising the steps of: a step 1 of applying a negative electrode paste to a negative electrode current collector to prepare a coating film, and then rolling the coating film, wherein the negative electrode paste contains a negative electrode active material containing a carbon material and a Si-based material, and a pore-forming material; and a 2 nd step of, after the 1 st step, performing a heat treatment on the coating film to decompose/gasify the pore-forming material, thereby forming a negative electrode composite material layer, wherein the pore size distribution of the negative electrode composite material layer measured by a mercury intrusion method has 2 peaks R1 and R2, the peak R1 is 0.5 μm or more and 1.5 μm or less, the peak R2 is 2 μm or more and 10 μm or less, the average particle diameter of the Si-based material is 4 μm or more, and the content of the Si-based material is 30 mass% or more with respect to the total amount of the negative electrode active material.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present disclosure, there may be provided: a negative electrode for a secondary battery, and a method for manufacturing a negative electrode for a secondary battery, wherein the negative electrode has a high capacity, and wherein expansion of the negative electrode is suppressed, and further, degradation of charge-discharge cycle characteristics is suppressed.
Drawings
Fig. 1 is a cross-sectional view of a secondary battery as an example of an embodiment.
Detailed Description
The negative electrode for a secondary battery, which is one embodiment of the present disclosure, is provided with: and a negative electrode composite material layer disposed on the negative electrode current collector, wherein the negative electrode composite material layer has a negative electrode active material containing a carbon material and a Si-based material, and the pore size distribution of the negative electrode composite material layer measured by mercury intrusion method has 2 peaks R1 and R2, wherein the peak R1 is 0.5 μm or more and 1.5 μm or less, the peak R2 is 2 μm or more and 10 μm or less, the average particle diameter of the Si-based material is 4 μm or more, and the content of the Si-based material is 30 mass% or more with respect to the total amount of the negative electrode active material. As is presumed in the present disclosure, the negative electrode composite material layer having 2 peaks (R1, R2) in the pore size distribution satisfying the above range forms pores most suitable for improvement of the permeability of the electrolyte or absorption of expansion and contraction of the Si-based material accompanied by charge and discharge, and therefore, can realize a high capacity of the battery and suppression of expansion of the negative electrode. However, if R1 and R2 are set in an appropriate range, the effect of suppressing the deterioration of the charge-discharge cycle characteristics cannot be sufficiently obtained due to the side reaction between the Si-based material and the electrolyte if the average particle diameter of the Si-based material is too small. Further, even if R1 and R2 are set in an appropriate range, if the content of the Si-based material is too small, the capacity of the battery cannot be increased. Therefore, by setting all of the parameters of the average particle diameter and the content of the 2 peaks R1, R2 and the Si-based material in the pore size distribution of the negative electrode composite material layer measured by the mercury intrusion method to the above-described proper ranges, the effect of achieving a high capacity, suppressing the expansion of the negative electrode, and further suppressing the deterioration of the charge-discharge cycle characteristics can be exhibited for the first time.
Hereinafter, embodiments of a negative electrode active material for a secondary battery and a secondary battery according to the present disclosure will be described in detail with reference to the drawings.
An example of a secondary battery as an embodiment of the present disclosure will be described below.
Fig. 1 is a cross-sectional view of a secondary battery as an example of an embodiment. The secondary battery 10 shown in fig. 1 includes: the positive electrode 11 and the negative electrode 12 are wound with a separator 13 interposed therebetween, a wound electrode body 14, an electrolyte, insulating plates 18 and 19 disposed on the upper and lower sides of the electrode body 14, and a battery case 15 for housing the above components. The battery case 15 is composed of a case main body 16 having a bottomed cylindrical shape and a sealing body 17 closing an opening of the case main body 16. Instead of the wound electrode body 14, an electrode body of another form such as a laminated electrode body in which positive and negative electrodes are alternately laminated with a separator interposed therebetween may be used. The battery case 15 may be a metal case such as a cylindrical case, a square case, a coin case, or a button case, a resin case formed by laminating resin sheets (so-called laminate type), or the like.
The electrolyte may be an aqueous electrolyte, but is preferably a nonaqueous electrolyte containing a nonaqueous solvent and an electrolyte salt dissolved in the nonaqueous solvent. Examples of the nonaqueous solvent include esters, ethers, nitriles, amides, and mixtures of 2 or more thereof. The nonaqueous solvent may contain a halogen substituent in which at least a part of hydrogen in the solvent is substituted with a halogen atom such as fluorine. Use of, for example, liPF in electrolyte salts 6 And lithium salts.
The case main body 16 is, for example, a metal container having a bottomed cylindrical shape. A gasket 28 is provided between the case main body 16 and the sealing body 17 to ensure tightness of the battery interior. The case main body 16 has, for example, a protruding portion 22 with a part of the side surface portion protruding inward for supporting the sealing body 17. The protruding portion 22 is preferably formed in a ring shape along the circumferential direction of the case main body 16, and the sealing body 17 is supported by the upper surface thereof.
The sealing body 17 has: a partially open metal plate 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cover 27 are laminated in this order from the electrode body 14 side. The members constituting the sealing body 17 have, for example, a disk shape or a ring shape, and the members other than the insulating member 25 are electrically connected to each other. The lower valve body 24 and the upper valve body 26 are connected to each other at respective central portions, and an insulating member 25 is interposed between respective peripheral portions. When the internal pressure of the secondary battery 10 rises due to heat generation caused by an internal short circuit or the like, for example, the lower valve body 24 deforms and breaks so as to push the upper valve body 26 toward the lid 27 side, and the current path between the lower valve body 24 and the upper valve body 26 is blocked. When the internal pressure further increases, the upper valve body 26 breaks, and the gas is discharged from the opening of the cover 27.
In the secondary battery 10 shown in fig. 1, the positive electrode lead 20 attached to the positive electrode 11 extends to the sealing body 17 side through the through hole of the insulating plate 18, and the negative electrode lead 21 attached to the negative electrode 12 extends to the bottom side of the case main body 16 through the outside of the insulating plate 19. The positive electrode lead 20 is connected to the lower surface of the partially opened metal plate 23, which is the bottom plate of the sealing body 17, by welding or the like, and the cap 27, which is the top plate of the sealing body 17 electrically connected to the partially opened metal plate 23, serves as a positive electrode terminal. The negative electrode lead 21 is connected to the bottom inner surface of the case main body 16 by welding or the like, and the case main body 16 serves as a negative electrode terminal.
The positive electrode 11, the negative electrode 12, and the separator 13 will be described in detail below.
[ Positive electrode ]
The positive electrode 11 includes a positive electrode current collector and a positive electrode composite material layer disposed on the positive electrode current collector. As the positive electrode current collector, a foil of a metal such as aluminum that is stable in the potential range of the positive electrode 11, a thin film having the metal disposed on the surface layer, or the like can be used. The positive electrode composite material layer is composed of, for example, a positive electrode active material, a binder, a conductive material, and the like. The positive electrode 11 can be produced, for example, as follows: the positive electrode current collector may be produced by applying a positive electrode paste containing a positive electrode active material, a binder, a conductive material, and the like to the surface of the positive electrode current collector, drying the coating film, and then rolling the coating film to form a positive electrode composite material layer on both sides of the positive electrode current collector.
As the conductive material contained in the positive electrode composite material layer, carbon materials such as carbon black, acetylene black, ketjen black, graphite, and carbon nanotubes can be exemplified. Examples of the binder contained in the positive electrode composite layer include a fluororesin such as Polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide, an acrylic resin, a polyolefin, a cellulose derivative such as styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC) or a salt thereof, polyethylene oxide (PEO), and the like.
As the positive electrode active material, for example, a lithium transition metal composite oxide or the like is used. The metal element contained in the lithium transition metal composite oxide includes Ni, co, mn, al, B, mg, ti, V, cr, fe, cu, zn, ga, sr, zr, nb, in, sn, ta, W and the like. Among them, at least 1 of Ni, co and Mn is preferably contained. Examples of suitable lithium transition metal composite oxides include those of the general formula LiMO 2 (M is Ni and X, X is a metal element other than Ni, the ratio of Ni relative to the total of metal elements other than LiA molar amount of 50 mol% or more and 95 mol% or less). Examples of X in the above formula include Co, mn, al, B, mg, ti, V, cr, fe, cu, zn, ga, sr, zr, nb, in, sn, ta, W.
[ negative electrode ]
The negative electrode 12 has a negative electrode current collector and a negative electrode composite material layer disposed on the negative electrode current collector. As the negative electrode current collector, a foil of a metal such as copper that is stable in the potential range of the negative electrode 12, a thin film having the metal disposed on the surface layer, or the like can be used. The negative electrode composite material layer contains a negative electrode active material, and may contain a binder, a conductive material, or the like. The negative electrode active material contains a carbon material and a Si-based material. The negative electrode active material may contain a substance capable of reversibly absorbing and releasing lithium ions in addition to the carbon material and the Si-based material. The binder and the conductive material may be the same as those of the positive electrode 11.
The pore size distribution of the anode composite layer measured by mercury intrusion method has 2 peaks R1 and R2. The peak value R1 is from 0.5 μm to 1.5 μm, and the peak value R2 is from 2 μm to 10 μm.
In the mercury porosimetry, mercury is pressurized to impregnate the pores of a solid sample, and the diameter and volume (volume) of the pores are calculated from the pressure applied to mercury and the amount of mercury pressed into the pores. When mercury having a pressure P is applied to the hole having the immersion diameter D, the diameter D of the hole is obtained from the pressure P, the contact angle θ of mercury, and the surface tension σ of mercury according to the following equation. In addition, the pore volume was calculated from the amount of mercury pressed into the pores. In the present disclosure, the pore diameter refers to the diameter of the pore.
-4σcosθ＝PD
The pore size distribution measured by mercury intrusion is a plot of Log differential pore volume (cm) for the average pore diameter (μm) of the region of each measurement site 3 Graph obtained in/g), with the pore diameter (. Mu.m) on the horizontal axis and the Log differential pore volume (. Cm) on the vertical axis 3 /g). Here, in the present disclosure, the peak in the pore size distribution refers to the pore size of the peak apex in the pore size distribution.
The peak value R1 may be 0.5 μm or more and 1.5 μm or less, and is preferably 0.8 μm or more and 1.2 μm or less, for example. If the peak value R1 is less than 0.5 μm, small pores exist in large numbers among particles in the negative electrode composite material layer, and therefore, the permeability of the electrolyte decreases, and the secondary battery cannot have a high capacity. If the peak value R1 exceeds 1.5 μm (less than 2 μm), the density of the negative electrode active material decreases, and the capacity of the secondary battery cannot be increased. The peak value R2 may be 2 μm or more and 10 μm or less, and is preferably 4 μm or more and 8 μm or less, for example. If the peak R2 is less than 2 μm, pores capable of absorbing expansion and contraction of the Si-based material accompanied by charge and discharge are small in the negative electrode composite material layer, and therefore expansion of the negative electrode cannot be suppressed. If the peak value R2 is 10 μm or more, large pores exist in a large amount in the negative electrode composite material layer, and therefore, the density of the negative electrode active material is reduced, and the secondary battery cannot have a high capacity.
The measurement of pore size distribution by mercury intrusion method was performed on the negative electrode composite material layer before initial charging. For example, a measurement sample obtained by punching a negative electrode for a secondary battery into a predetermined shape before initial charging is used, and the pore size distribution of the negative electrode composite material layer included in the measurement sample can be measured by mercury intrusion method. The measurement sample may have a negative electrode composite material layer at least on the surface thereof, or may have another structure such as a negative electrode current collector.
The pore size distribution by the mercury intrusion method can be measured by using an apparatus such as AutoPore IV9500 series manufactured by Micromeritics Instrument Corporation. In the measurement, a measurement sample is sealed in a sample container under an inert atmosphere, mercury is injected into the sample container, and pressure is applied to the mercury. Here, the pressure applied to mercury is appropriately adjusted according to the pore size that the measurement sample can have, and is not particularly limited, and it is preferable to change the pressure from 0.5psi (3.4 kPa) to 60000psi (413400 kPa) and measure the pore size in a wide range, for example.
As described above, in order to achieve a high capacity of the secondary battery, to suppress expansion of the negative electrode, and to suppress deterioration of charge-discharge cycle characteristics, it is necessary to set the content and average particle diameter of the Si-based material to an appropriate range in addition to the peak value R1 of 0.5 μm or more and 1.5 μm or less and the peak value R2 of 2 μm or more and 10 μm or less. The Si-based material and the carbon material contained in the negative electrode active material will be described below.
The Si-based material contained in the negative electrode active material is not particularly limited as long as it can reversibly store and release lithium ions and the like, and examples thereof include Si particles, si-containing alloy particles, si compound particles, and the like. These may be used alone or in combination of 2 or more.
The Si particles may be obtained by a gas phase method, or by micro-pulverizing silicon chips, or may be produced by any method. Examples of the Si-containing alloy particles include alloys containing Si and containing an alkali metal, an alkaline earth metal, a transition metal, a rare earth metal, or a metal selected from the group consisting of combinations thereof. Examples of the Si compound particles include Si compound particles having a silicate phase and Si particles dispersed in the silicate phase, si compound particles having a silicon oxide phase and Si particles dispersed in the silicon oxide phase, si compound particles having a carbon phase and Si particles dispersed in the carbon phase, and the like. Among them, in terms of increasing the capacity of the secondary battery, suppressing the deterioration of charge-discharge cycle characteristics, and the like, si compound particles having a silicate phase and Si particles dispersed in the silicate phase, and Si compound particles having a carbon phase and Si particles dispersed in the carbon phase are preferable.
For example, the silicate phase preferably contains at least 1 element selected from lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, and palladium in view of high lithium ion conductivity. Among them, the silicate phase preferably contains a lithium silicate phase (hereinafter, may be referred to as a lithium silicate phase) in terms of high lithium ion conductivity.
The lithium silicate phase is for example of the formula: li (Li) 2z SiO 2+z (0<z<2) And (3) representing. From the viewpoints of stability, ease of production, lithium ion conductivity, and the like, z preferably satisfies 0<z<A relationship of 1, more preferably z=1/2.
Si compound particles having Si particles dispersed in the silicon oxide phase are, for example, a silicon oxide having the general formula SiO x (preferably 0)<x<2 is in the range of,More preferably, the range of 0.5.ltoreq.x.ltoreq.1.6). The Si compound particles having Si particles dispersed in the carbon phase are, for example, those of the formula SixC1y (preferably 0<x is less than or equal to 1 and 0<The range of y.ltoreq.1, more preferably the range of 0.3.ltoreq.x.ltoreq.0.45 and 0.7.ltoreq.y.ltoreq.0.55).
Preferably, a conductive coating film made of a material having high conductivity is formed on the particle surfaces of the Si-based material. As the conductive film, a metal compound film, and the like can be given, and a carbon film is preferable in terms of electrochemical stability and the like. The carbon coating film may be formed by, for example, a CVD method using acetylene, methane, or the like, a method in which coal pitch, petroleum pitch, a phenolic resin, or the like is mixed with a silicon-based active material and heat-treated. Further, an electroconductive filler such as carbon black may be fixed to the particle surfaces of the Si-based material with a binder to form an electroconductive film.
The content of the Si-based material may be 30 mass% or more with respect to the total amount of the negative electrode active material in terms of, for example, increasing the capacity of the secondary battery. In order to achieve a higher capacity of the secondary battery and further suppress expansion of the negative electrode, the content of the Si-based material is preferably 30 mass% or more and 60 mass% or less, more preferably 35 mass% or more and 55 mass% or less, relative to the total amount of the negative electrode active material.
The average particle diameter of the Si-based material may be 4 μm or more, for example, in order to suppress a decrease in charge-discharge cycle characteristics due to side reactions with the electrolyte. In addition, in order to suppress the deterioration of the charge-discharge cycle characteristics and further suppress the expansion of the negative electrode, the average particle diameter of the Si-based material is, for example, preferably 4 μm or more and 12 μm or less, and more preferably 6 μm or more and 10 μm or less.
The carbon material contained in the negative electrode active material may be, for example, a conventionally known carbon material used as a negative electrode active material of a secondary battery, but in terms of further suppressing a decrease in charge-discharge cycle characteristics, for example, natural graphite such as flake graphite, bulk graphite, or soil-like graphite, graphite such as bulk artificial graphite (MAG), or artificial graphite such as graphitized Mesophase Carbon Microbeads (MCMB) are preferable.
The average particle diameter of the carbon material is preferably 10 μm or more and 25 μm or less, more preferably 12 μm or more and 20 μm or less, for example, in order to further suppress expansion of the negative electrode.
The average particle diameter of each material was a volume average particle diameter D50 having a volume accumulation value of 50% in the particle size distribution obtained by the laser diffraction scattering method.
The content of the carbon material is, for example, preferably 40% by mass or more and 70% by mass or less, more preferably 45% by mass or more and 65% by mass or less, relative to the total amount of the anode active material.
An example of a method for manufacturing the negative electrode 12 will be described. The method for manufacturing the negative electrode 12 includes the steps of: a step 1 of applying a negative electrode paste containing a negative electrode active material containing a carbon material and a Si-based material, a pore-forming material, and a binder, etc. if necessary, to a negative electrode current collector to prepare a coating film, and then rolling the coating film; and a step 2 of heating the coating film after the step 1 to decompose/gasify the pore-forming material, thereby forming a negative electrode composite material layer. The average particle diameters and the content of the Si-based material and the carbon material are as described above, and therefore omitted.
By heat-treating the coating film to decompose/gasify (e.g., sublimate) the pore-forming material, the pore-forming material is released from the coating film, whereby not only small pores but also relatively large pores can be formed between the particles in the anode composite layer. By thus subjecting the anode paste to which the pore-forming material is added to a heat treatment, the pore distribution of the anode composite material layer has a peak value R1 of 0.5 μm or more and 1.5 μm or less and a peak value R2 of 2 μm or more and 10 μm or less. On the other hand, if a negative electrode paste containing no pore-forming material is used, small pores are formed only between particles in the resulting negative electrode composite material layer. Therefore, when a negative electrode paste to which no pore-forming material is added is used, the pore distribution of the negative electrode composite material layer generally has a peak value R1 of 0.5 μm or more and 1.5 μm or less.
The heating treatment temperature is not particularly limited as long as it is a temperature at which decomposition/vaporization of the pore-forming material occurs. The heating treatment time may be, for example, 5 hours or more, as long as it is sufficient to ensure the decomposition/vaporization of the pore-forming material in the coating film.
As the pore-forming material, a known one can be used. Examples of the pore-forming material include metallic oxalate, camphor, naphthalene, and the like. Further, as the pore-forming material, for example, dicarboxylic acids such as fumaric acid, malonic acid, and malic acid may be used. The average particle diameter of the pore-forming material is preferably, for example, 2 μm or more and 10 μm or less. By setting the average particle diameter of the pore-forming material to the above range, it becomes easy to control the peak value R2 in the pore diameter distribution of the anode composite material layer to a range of 2 μm to 10 μm. When a pore-forming material having an average particle diameter falling outside the above range is used, the peak values R2 and R1 in the pore size distribution of the anode composite material layer can be controlled by adjusting the average particle diameter of each material used in the anode active material, the viscosity of the anode paste by solvent addition or the like, the heating treatment time, the temperature, the line pressure during film coating and the like.
Examples of the mixing of the raw materials such as the negative electrode active material, the pore-forming material, and the binder in obtaining the negative electrode paste include a chopper, a pin mill, a bead mill, a microparticle compounding device (a device that generates a shearing force between a rotor having a special shape and a collision plate that rotates at a high speed in a tank), a granulator, a twin-screw extrusion kneader, and a kneader such as a planetary mixer.
The negative electrode paste is applied using, for example, a slot die coater, a reverse roll coater, a lip coater, a blade coater, a gravure coater, a dip coater, or the like.
When the negative electrode paste is applied to the negative electrode current collector to obtain a coating film, the coating film is preferably dried by heating. The temperature of the heat drying is desirably a temperature at which decomposition/vaporization of the pore-forming material does not occur, but a part of the pore-forming material may be decomposed/vaporized by the heat drying.
The coating film may be rolled by a roll press at a predetermined line pressure, for example, a plurality of times until the coating film has a predetermined thickness.
[ separator ]
For example, a porous sheet having ion permeability and insulation is used as the separator 13. Specific examples of the porous sheet include microporous films, woven fabrics, and nonwoven fabrics. As the material of the separator 13, polyolefin such as polyethylene and polypropylene, cellulose, and the like are suitable. The separator 13 may have a single-layer structure or a laminated structure. A heat-resistant layer or the like may be formed on the surface of the separator.
Examples
The present disclosure is further described below with reference to examples, but the present disclosure is not limited to these examples.
Example 1 >
[ production of negative electrode ]
The mass ratio of graphite particles having an average particle diameter of 17 μm to Si-based material having an average particle diameter of 8 μm in which Si particles are dispersed in a carbon phase was 50: 50. The mixture was used as a negative electrode active material. Then, with a negative electrode active material: carboxymethyl cellulose (CMC): styrene-butadiene copolymer rubber (SBR): multilayer carbon nanotubes: the mass ratio of fumaric acid (average particle diameter 6 μm) was 100:1:1:1:12.5 mixing them with any water to prepare a negative electrode paste. The negative electrode paste was applied to both surfaces of a negative electrode current collector made of copper foil, and after drying the coating film, the coating film was rolled by a rolling roll. Thereafter, the coating film was subjected to heat treatment at 200 ℃ for 5 hours, thereby producing a negative electrode having a negative electrode composite material layer formed on both sides of a negative electrode current collector.
In the negative electrode obtained, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and as a result, 2 peaks R1 and R2 were shown, the peak value R1 being 1 μm and the peak value R2 being 6 μm.
[ production of Positive electrode ]
By LiCo 1/3 Mn 1/3 Ni 1/3 O 2 The lithium transition metal composite oxide shown: acetylene black: the mass ratio of the polyvinylidene fluoride is 98:1:1, and adding N-methyl-2-pyrrolidone (NMP) to prepare a positive electrode paste. The negative electrode paste was applied to both sides of an aluminum foil, and after drying the coating film, the coating film was rolled by a rolling roll to prepare a shape on both sides of a positive electrode current collectorForming the positive electrode with the positive electrode composite material layer.
[ preparation of nonaqueous electrolyte solution ]
Making LiPF 6 Dissolved at a concentration of 1mol/L in a solution of 1:3 in a mixed solvent of Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC), and not preparing a water electrolyte.
[ production of test Battery cell ]
The positive electrode and the negative electrode were laminated so as to face each other via a separator made of polyolefin, and wound to produce an electrode body. Next, the electrode body was housed in a bottomed cylindrical battery case body, and after the nonaqueous electrolyte was injected, the opening of the battery case body was sealed with a gasket and a sealing member, thereby producing a test battery cell.
Example 2 >
A negative electrode was produced in the same manner as in example 1, except that fumaric acid having an average particle diameter of 2 μm was used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of example 2, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and as a result, it was shown that 2 peaks R1 and R2 were obtained, the peak value R1 was 1 μm and the peak value R2 was 2 μm.
Example 3 >
A negative electrode was produced in the same manner as in example 1, except that fumaric acid having an average particle diameter of 10 μm was used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of example 3, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and the result showed 2 peaks R1 and R2, with peak R1 being 1 μm and peak R2 being 10 μm.
Example 4 >
The mass ratio of graphite particles having an average particle diameter of 17 μm to Si-based material having an average particle diameter of 8 μm in which Si particles are dispersed in a carbon phase was 70:30, a negative electrode was produced in the same manner as in example 1, and a test battery cell was produced in the same manner as in example 1, except that the negative electrode was used. In the negative electrode of example 4, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and the result showed 2 peaks R1 and R2, with peak R1 being 1 μm and peak R2 being 6 μm.
Example 5 >
The mass ratio of graphite particles having an average particle diameter of 17 μm to Si-based material having an average particle diameter of 8 μm in which Si particles are dispersed in a carbon phase was 40:60, a negative electrode was produced in the same manner as in example 1, and a test battery cell was produced in the same manner as in example 1, except that the negative electrode was used. In the negative electrode of example 5, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and the result showed 2 peaks R1 and R2, with peak R1 being 1 μm and peak R2 being 6 μm.
Example 6 >
A negative electrode was produced in the same manner as in example 1, except that a Si-based material having Si particles with an average particle diameter of 4 μm dispersed in a carbon phase was used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of example 6, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and the result showed 2 peaks R1 and R2, with peak R1 being 1 μm and peak R2 being 6 μm.
Example 7 >
A negative electrode was produced in the same manner as in example 1, except that a Si-based material having Si particles with an average particle diameter of 12 μm dispersed in a carbon phase was used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of example 7, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and the result showed 2 peaks R1 and R2, with peak R1 being 1 μm and peak R2 being 6 μm.
Example 8 >
A negative electrode was produced in the same manner as in example 1, except that graphite particles having an average particle diameter of 10 μm were used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of example 8, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and the result showed 2 peaks R1 and R2, with peak R1 being 1 μm and peak R2 being 6 μm.
Example 9 >
A negative electrode was produced in the same manner as in example 1, except that graphite particles having an average particle diameter of 25 μm were used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of example 8, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and the result showed 2 peaks R1 and R2, with peak R1 being 1 μm and peak R2 being 6 μm.
Example 10 >
The mass ratio of graphite particles having an average particle diameter of 17 μm to Si-based material having an average particle diameter of 8 μm in which Si particles are dispersed in a carbon phase was 30:70, a negative electrode was produced in the same manner as in example 1, and a test battery cell was produced in the same manner as in example 1, except that the negative electrode was used. In the negative electrode of example 10, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and the result showed 2 peaks R1 and R2, with peak R1 being 1 μm and peak R2 being 6 μm.
Example 11 >
A negative electrode was produced in the same manner as in example 1, except that a Si-based material having Si particles with an average particle diameter of 14 μm dispersed in a carbon phase was used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of example 11, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and as a result, it was shown that 2 peaks R1 and R2 were obtained, the peak value R1 was 1 μm and the peak value R2 was 6 μm.
Example 12 >
A negative electrode was produced in the same manner as in example 1, except that graphite particles having an average particle diameter of 8 μm were used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of example 12, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and the result showed 2 peaks R1 and R2, with peak R1 being 1 μm and peak R2 being 6 μm.
Example 13 >
A negative electrode was produced in the same manner as in example 1, except that graphite particles having an average particle diameter of 40 μm were used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of example 12, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and the result showed 2 peaks R1 and R2, with peak R1 being 1 μm and peak R2 being 6 μm.
Comparative example 1 >
A negative electrode was produced in the same manner as in example 1, except that fumaric acid having an average particle diameter of 12 μm was used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of comparative example 1, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and as a result, 2 peaks R1 and R2 were shown, the peak value R1 was 1 μm and the peak value R2 was 12 μm.
Comparative example 2 >
A negative electrode was produced in the same manner as in example 1, except that fumaric acid having an average particle diameter of 1 μm was used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of comparative example 2, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion, and as a result, 1 peak value R1 was shown, and the peak value R1 was 1 μm.
Comparative example 3 >
A negative electrode was produced in the same manner as in example 1, except that fumaric acid was not used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of comparative example 3, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion, and as a result, 1 peak value R1 was shown, and the peak value R1 was 1 μm.
Comparative example 4 >
The mass ratio of graphite particles having an average particle diameter of 17 μm to Si-based material having an average particle diameter of 8 μm in which Si particles are dispersed in a carbon phase was 80:20, a negative electrode was produced in the same manner as in example 1, and a test battery cell was produced in the same manner as in example 1, except that the negative electrode was used. In the negative electrode of comparative example 4, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and as a result, 2 peaks R1 and R2 were shown, the peak value R1 was 1 μm and the peak value R2 was 6 μm.
Comparative example 5 >
A negative electrode was produced in the same manner as in example 1, except that a Si-based material having Si particles with an average particle diameter of 3 μm dispersed in a carbon phase was used, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of comparative example 5, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion, and as a result, 2 peaks R1 and R2 were shown, with peak R1 being 1 μm and peak R2 being 6 μm.
Comparative example 6 >
A negative electrode was produced in the same manner as in example 1, except that the compressive force of the coating film by rolling was increased, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of comparative example 6, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and as a result, it was shown that 2 peaks R1 and R2 were present, the peak value R1 was 0.3 μm and the peak value R2 was 6 μm.
Comparative example 7 >
A negative electrode was produced in the same manner as in example 1, except that the compressive force of the coating film by rolling was reduced, and a test battery cell was produced in the same manner as in example 1. In the negative electrode of comparative example 7, the pore size distribution of the negative electrode composite material layer was measured by mercury intrusion method, and as a result, it was shown that 2 peaks R1 and R2 were present, the peak value R1 was 1.7 μm and the peak value R2 was 6 μm.
[ evaluation of Battery Capacity ]
For the test battery cells of each example and each comparative example, charging was performed at a constant current of 0.5C under a temperature environment of 25 ℃ until the battery voltage became 4.2V, and thereafter charging was performed at a constant voltage of 4.2V until the current value became 0.05C. Thereafter, discharge was performed at a constant current of 0.2C until the battery voltage became 2.5V. The discharge capacity at this time was taken as a battery capacity, and the results are summarized in table 1.
[ charge-discharge cycle test ]
For the test battery cells of each example and each comparative example, charging was performed at a constant current of 0.5C under a temperature environment of 25 ℃ until the battery voltage became 4.2V, and thereafter charging was performed at a constant voltage of 4.2V until the current value became 0.05C. Thereafter, discharge was performed at a constant current of 0.5C until the battery voltage became 2.5V. The charge and discharge were performed for 50 cycles, and the capacity retention rate in the charge and discharge cycle was determined by the following formula, and the results thereof are summarized in table 1.
Capacity maintenance ratio (%) = (discharge capacity of 50 th cycle/discharge capacity of 1 st cycle) ×100
[ evaluation of negative electrode expansion Rate ]
For each of the test battery cells of examples and comparative examples, the battery cells were charged at a constant current of 1/3C under a temperature environment of 25℃until the battery voltage became 4.2V, and thereafter, the battery cells were charged at a constant voltage of 4.2V until the current value became 0.05C. And decomposing the charged test battery unit, taking out the negative electrode, and measuring the thickness of the charged negative electrode by using a micrometer. Then, the negative electrode expansion ratio was calculated by the following formula, and the results thereof are summarized in table 1.
Negative electrode expansion ratio (%) = (negative electrode thickness after charging/negative electrode thickness when manufacturing negative electrode) ×100
TABLE 1
As shown in table 1, the battery capacities of examples 1 to 13 were 500mAh or more, the capacity retention rates after 50 cycles were 95% or more, and the expansion rates of the negative electrodes were lower than 140%. On the other hand, the battery capacities of comparative examples 1 to 7 were lower than 500mAh, the capacity retention rate after 50 cycles was lower than 90%, and the expansion rate of the negative electrode was 140% or more. That is, in the negative electrode composite material layer including the negative electrode active material containing the carbon material and the Si-based material, the negative electrode has a pore size distribution as measured by the mercury porosimetry, having 2 peaks R1 and R2, the peak R1 being 0.5 μm or more and 1.5 μm or less, the peak R2 being 2 μm or more and 10 μm or less, the average particle diameter of the Si-based material being 4 μm or more, and the content of the Si-based material being 30 mass% or more with respect to the total amount of the negative electrode active material, whereby the battery can be increased in capacity, swelling of the negative electrode can be suppressed, and deterioration of charge-discharge cycle characteristics can be suppressed.
Description of the reference numerals
10 secondary battery, 11 positive electrode, 12 negative electrode, 13 separator, 14 electrode body, 15 battery case, 16 case main body, 17 sealing body, 18 insulating plate, 18, 19 insulating plate, 20 positive electrode lead, 21 negative electrode lead, 22 protruding portion, 23 partially open metal plate, 24 lower valve body, 25 insulating member, 26 upper valve body, 27 cover, 28 gasket.
Claims (9)
1. A negative electrode for a secondary battery, comprising: a negative electrode current collector and a negative electrode composite material layer disposed on the negative electrode current collector,
the negative electrode composite material layer has a negative electrode active material containing a carbon material and a Si-based material,
the pore size distribution of the negative electrode composite material layer measured by mercury intrusion method has 2 peaks R1 and R2,
the peak value R1 is from 0.5 μm to 1.5 μm, the peak value R2 is from 2 μm to 10 μm,
the average particle diameter of the Si-based material is 4 [ mu ] m or more, and the content of the Si-based material is 30 mass% or more relative to the total amount of the negative electrode active material.
2. The negative electrode for secondary battery according to claim 1, wherein the Si-based material comprises: a Si compound having a silicate phase and Si particles dispersed within the silicate phase.
3. The negative electrode for secondary battery according to claim 1 or 2, wherein the Si-based material comprises: a Si compound having a carbon phase and Si particles dispersed in the carbon phase.
4. The negative electrode for a secondary battery according to any one of claims 1 to 3, wherein the content of the Si-based material is 30 mass% or more and 60 mass% or less relative to the total amount of the negative electrode active material.
5. The negative electrode for secondary batteries according to any one of claims 1 to 4, wherein the Si-based material has an average particle diameter of 4 μm or more and 12 μm or less.
6. The negative electrode for a secondary battery according to any one of claims 1 to 5, wherein the carbon material comprises graphite.
7. The negative electrode for secondary batteries according to any one of claims 1 to 6, wherein the carbon material has an average particle diameter of 10 μm or more and 25 μm or less.
8. A secondary battery comprising the negative electrode for a secondary battery according to any one of claims 1 to 7.
9. A method for manufacturing a negative electrode for a secondary battery, comprising the steps of:
a step 1 of applying a negative electrode paste to a negative electrode current collector, wherein a coating film is produced, and then the coating film is rolled, wherein the negative electrode paste contains a negative electrode active material containing a carbon material and a Si-based material, and a pore-forming material; and, a step of, in the first embodiment,
a step 2 of performing a heat treatment on the coating film after the step 1 to decompose/gasify the pore-forming material, thereby forming a negative electrode composite material layer,
the pore size distribution of the negative electrode composite material layer measured by mercury intrusion method has 2 peaks R1 and R2,
the peak value R1 is from 0.5 μm to 1.5 μm, the peak value R2 is from 2 μm to 10 μm,
the average particle diameter of the Si-based material is 4 [ mu ] m or more, and the content of the Si-based material is 30 mass% or more relative to the total amount of the negative electrode active material.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2021073909 | 2021-04-26 | ||
| JP2021-073909 | 2021-04-26 | ||
| PCT/JP2022/017625 WO2022230661A1 (en) | 2021-04-26 | 2022-04-12 | Secondary battery negative electrode, secondary battery, and method for manufacturing secondary battery negative electrode |
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| CN117178384A true CN117178384A (en) | 2023-12-05 |
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| Country | Link |
|---|---|
| EP (1) | EP4333106A1 (en) |
| JP (1) | JPWO2022230661A1 (en) |
| CN (1) | CN117178384A (en) |
| WO (1) | WO2022230661A1 (en) |
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| KR100818263B1 (en) * | 2006-12-19 | 2008-03-31 | 삼성에스디아이 주식회사 | Porous anode active material, method of preparing the same, and anode and lithium battery containing the material |
| KR20140105794A (en) * | 2011-12-02 | 2014-09-02 | 도요타지도샤가부시키가이샤 | Lithium secondary battery and method for manufacturing same |
| JP5827977B2 (en) | 2013-07-30 | 2015-12-02 | 住友ベークライト株式会社 | Negative electrode active material for lithium ion secondary battery, negative electrode mixture for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
| JP6897507B2 (en) * | 2017-11-09 | 2021-06-30 | トヨタ自動車株式会社 | Non-aqueous electrolyte secondary battery and its manufacturing method |
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- 2022-04-12 EP EP22795575.4A patent/EP4333106A1/en active Pending
- 2022-04-12 CN CN202280028935.3A patent/CN117178384A/en active Pending
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| WO2022230661A1 (en) | 2022-11-03 |
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